Organic Electronics 122 (2023) 106909

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Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Comparative studies on frontier orbitals, molecular packing and

optoelectronic properties of ambipolar polymer semiconductors based on
bisthiophene-fused diketopyrrolopyrrole
Lanchao Ma a, *, Zhengang Li a, Bing Chen b, Xiaojian Zheng c, Haiying Xie a, Chengliang Ji a,
Xiaowei Zhan c, Yunqi Liu d, Xingguo Chen b, **
a
College of New Materials and Chemical Engineering, Beijing Key Laboratory of Special Elastomer Composite Materials, Beijing Institute of Petrochemical Technology,
Beijing, 102617, China
b
Hubei Key Laboratory on Organic and Polymeric Optoelectronic Materials, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China
c
School of Materials Science and Engineering, Peking University, Beijing, 100871, China
d
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

A R T I C L E I N F O A B S T R A C T

Keywords:
Ambipolar polymer semiconductors
Bisthiophene-fused diketopyrrolopyrrole
Organic field-effect transistors
Ambipolar field-effect transistors based on polymer semiconductors facilitate the convenient fabrication of low-
power complementary organic circuits. However, the species of ambipolar polymer semiconductors are limited;
the design and synthesis strategies are scarce. This work demonstrated that bisthiophene-fused diketopyrrolo­
pyrrole (DPPFu) was a wonderful building unit for ambipolar polymer semiconductors. Ambipolar polymer
semiconductors could be obtained by copolymerizing DPPFu with both electron-deficient comonomers and
electron-rich comonomers. P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) were synthesized by copolymerizing
DPPFu with thiophene, thienothiophene and benzothiadiazole, respectively. The structural variation of co­
monomers allowed for a systematic study on the relationship between comonomer structure, frontier orbital
energy level, orbital delocalization index, molecular packing, film morphology and the corresponding charge
transport properties. Thienothiophene endowed P(DPPFu-TT) with maximum orientation of edge-on packing.
The considerable delocalization extent of the lowest unoccupied molecular orbitals (LUMOs) for P(DPPFu-T) and
P(DPPFu-TT) resulted in pronounced electron transport property. P(DPPFu-TT) displayed the best charge
transport property with hole mobility up to about 0.1 cm2V− 1s− 1 and electron mobility of 7.5 × 10− 2 cm2V− 1s− 1.
P(DPPFu-BT) showed ideally balanced charge carrier mobilities for both holes and electrons of 1.6 × 10− 2
cm2V− 1s− 1 and 1.7 × 10− 2 cm2V− 1s− 1, respectively. Ion/Ioff ratios of all the ambipolar polymers were above
103. The ambipolarity of polymer semiconductors was related to not only push-pull electronic characteristics of
comonomers, but also the planarity of polymer backbones and delocalization extent of frontier orbitals. Overall,
this study provides valuable insights into the design and synthesis of ambipolar polymer semiconductors, which
is crucial for the advancement of low-power complementary organic circuits.

1. Introduction provides opportunities for low-cost fabrication of large-area flexible

Ambipolar field-effect transistors (FETs) facilitate the fabrication of
complementary logic circuits, and endow the integrated circuits with
low power dissipation, wide noise margins and high robustness [1–3].
As an important component for ambipolar FETs, the semiconductor
layer could conduct both electrons and holes. Polymer semiconductors
are of versatile chemical synthesis and solution processing, which
devices such as smart cards, bendable displays, and radiofrequency
identification (RFID) tags [4–7]. Consequently, ambipolar polymer
semiconductors are attracting more and more research interest.
Donor-acceptor (D-A) strategy is widely used in the design of high-
performance polymer semiconductors for FETs. D-A copolymers offer
significant potential in achieving tunable energy levels, robust intra­
molecular charge transfer (ICT), and intermolecular interactions

* Corresponding author.
** Corresponding author.
E-mail addresses: 0020150027@bipt.edu.cn (L. Ma), xgchen@whu.edu.cn (X. Chen).

https://doi.org/10.1016/j.orgel.2023.106909
Received 16 July 2023; Received in revised form 20 August 2023; Accepted 20 August 2023
Available online 22 August 2023
1566-1199/© 2023 Elsevier B.V. All rights reserved.
L. Ma et al.
between adjacent polymer chains. Among the most commonly used
donor moieties are thiophene and its derivatives; while lactam, imide
and thiazole derivatives are usually adopted as the acceptor units [8].
Charge transport property of polymer semiconductors could be
readily modulated by engineering the donor and acceptor units [9], and
the majority carrier type is determined by the relative strength of donor
and acceptor components [10]. For example, diketopyrrolopyrrole
(DPP)-thiophenes (Ts) copolymers, such as P(DPP-nT), exhibit varying
charge carrier types and mobility based on the number of thiophenes
present. Both P(DPP-2T) and P(DPP-3T) exhibit ambipolar charge
transport, with hole transport being dominant [11–13]. However, an
increase in the number of thiophenes enhances donor strength and re­
sults in unipolar hole transport with increased mobility [14–16]. To
enhance electron transport property, benzothiadiazole is incorporated.
The introduction of benzothiadiazole to P(DPP-2T) endows P
(DPP-2T-BT) with balanced ambipolar charge transport property [17].
The hole and electron mobilities of P(DPP-2T-BT) are 0.35 cm2V− 1s− 1
and 0.40 cm2V− 1s− 1, respectively. P(DPP-2T-bisBT), synthesized by
adding one more benzothiadiazole to P(DPP-2T-BT), exhibits
electron-dominant charge transport property and the electron mobility
is about one order of magnitude higher than the hole mobility [18].
Electron-withdrawing (or donating) ability could be enhanced by
incorporating more acceptor (donor) moieties. Except that, electron-
withdrawing ability could also be improved by incorporating more
electron withdrawing groups in the acceptor unit.
Thiadiazoloquinoxaline-fused acenaphthenequinone imide (TQAI) is a
highly π-expanded and sulfur/nitrogen enriched acceptor, a strong
electron deficient unit. A conjugated copolymer containing TQAI and
thiophene derivatives demonstrates ambipolar charge transport, with
electron mobility approximately 4 times higher than hole mobility [19].
The interplay between donor and acceptor strengths could tune the
electronic structure of polymer semiconductors, thus modulating charge
carrier type and transport property. Bisthiophene-fused DPP (DPPFu), a
building block comprising both DPP (with electron-withdrawing prop­
erties) and thiophenes (with electron-donating properties) [10,20–22],
has been utilized to construct ambipolar semiconductors.
PBDTT-DPPFu, consisting of benzo[1,2-b:4,5-b′]dithiophene (BDTT) as
the donor and DPPFu as the acceptor unit [20], was synthesized and
compared to the unfused counterpart, PBDTT-DPP. The hole mobility of
PBDTT-DPPFu was about 1.8 × 10− 3 cm2V− 1s− 1, which was over one
order of magnitude higher than that of PBDTT-DPP, while the electron
mobility of PBDTT-DPPFu was about 1.0 × 10− 2 cm2V− 1s− 1, which was
more than two times that of PBDTT-DPP. The results of UV–vis spec­
troscopy, DFT calculation, ESP and vdW analyses, as well as XRD
implied that ring-fusion methods provided a robust approach to
enhancing interchain interaction between chain segments in polymer
semiconductors.
In the construction of optoelectronic materials, DPPFu is often
employed as an electron acceptor and copolymerized with electron do­
nors to construct D-A copolymers [21]. However, systematic investiga­
tion of polymer semiconductors based on DPPFu remains limited. When
utilizing bisthiophene-fused DPP as a building block for copolymer
semiconductors, several issues require analysis: 1. How does the double
bond in the fused ring impact the spatial and electronic structure of the
DPPFu? 2. How does the structure of comonomers affect the spatial
configuration, molecular weight of the copolymers, and chain packing in
the thin films? 3. How does the electronic property of comonomers affect
the absorption spectra, frontier orbital energy levels, charge carrier type
and carrier mobility of the copolymer semiconductors?
In this work, DPPFu was synthesized by fusing the two N atoms in the
DPP unit with two flanking thiophenes, yielding a π-expanded, planar
fused-ring building block [21,23–25]. Additionally, 2-octyldodecyl side
chains were attached to the fused benzene rings to ensure good solubi­
lity of the building block. P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT)
were synthesized by copolymerizing DPPFu with thiophene, thieno­
thiophene and benzothiadiazole, respectively. The molecular weight,
2
Organic Electronics 122 (2023) 106909
absorption spectrum, energy levels, and frontier orbital distribution of
the copolymer semiconductors were compared. The relationship be­
tween the structure of copolymer semiconductors and their molecular
packing, film morphology and charge transport properties was also
systematically investigated.
2. Results and discussion
2.1. Molecular weight and thermal stability
DPPFu (bisthiophene-fused DPP dibromide) was synthesized ac­
cording to the previous references. [24,26] Thiophene ditin, thieno­
thiophene ditin and benzothiadiazole diboric acid ester were purchased
from Derthon Optoelectronics Materials Science Technology Co Ltd.
The synthetic routes for polymer semiconductors are depicted in
Scheme 1. P(DPPFu-T) and P(DPPFu-TT) were synthesized via Stille-
coupling polymerization of DPPFu dibromide with thiophene ditin and
thienothiophene ditin, respecctively; P(DPPFu-BT) was synthesized via
Suzuki-coupling of DPPFu dibromide with benzothiadiazole diborate.
The crude products were purified by Soxhlet extraction using methanol,
acetone, and hexane successively to elute low molecular weight oligo­
mers and other impurities. Chloroform was used as the end-product
solvent for P(DPPFu-T) and P(DPPFu-TT), whereas hexane was used
for P(DPPFu-BT). The number-average molecular weight (Mn), weight-
average molecular weight (Mw) and polydispersity index (Mw/Mn)
were listed in Table S1. The molecular weight of P(DPPFu-BT) was the
lowest among these polymers due to the low reaction temperature. The
reaction temperature for P(DPPFu-T) and P(DPPFu-TT) synthesis was
90 ◦ C, whereas it was 70 ◦ C for P(DPPFu-BT) synthesis. Higher reaction
temperatures provide more energy for the coupling reaction, while the
lower reaction temperature used for P(DPPFu-BT) synthesis supplies less
energy, thereby reducing the probability of coupling between DPPFu
dibromide and benzothiadiazole diborate, ultimately resulting in a
lower molecular weight. The Mn of polymer semiconductors featuring
DPPFu was often smaller than that of their unfused counterparts [20,
22]. The main reason was that the DPPFu was more rigid than its un­
fused counterpart and caused larger steric hindrance in the coupling
reaction. The polymer semiconductors exhibited high thermal stability,
with decomposition temperatures above 370 ◦ C.
2.2. DFT calculation
To predict how comonomers can impact the spatial and electronic
features of polymer semiconductors, theoretical calculations were per­
formed to evaluate the dihedral angels, frontier orbital energy and
orbital delocalization index (ODI) of these polymer semiconductors.
Density function theory (DFT) was employed in these calculations, and
geometries were optimized at the B3LYP level. For computational
simplicity, models comprising two repeating units (DPPFu-T_ × 2,
DPPFu-TT_ × 2 and DPPFu-BT_ × 2) were used, with branched alkyl
chains replaced with methyl groups (Fig. 1). The absence of bulky
branched alkyl chains resulted in all backbones exhibiting good copla­
narity. The dihedral angles between DPPFu and comonomers were
roughly 0.02◦ , 0.008◦ and 0.443◦ for DPPFu-T_ × 2, DPPFu-TT_ × 2 and
DPPFu-BT_ × 2, respectively. The dihedral angle in DPPFu-BT_ × 2 was
slightly larger than that in DPPFu-T_ × 2 and DPPFu-TT_ × 2. Addi­
tionally, the bond length between DPPFu and comonomers in DPPFu-
BT_ × 2 was about 0.02 Å longer than that in DPPFu-T_ × 2 and DPPFu-
TT_ × 2. The larger dihedral angle and longer bond length in DPPFu-BT_
× 2 could primarily be attributed to the steric hindrance caused by
benzothiadiazole. Upon the introduction of bulky side chains, the
dihedral angle between diketopyrrolopyrrole and fused thiophenes
remained stable, while the dihedral angle between DPPFu and co­
monomers likely increased.
Using geometry optimization, ODI was calculated via the Multiwfn
program with Hirshfeld method as the base [27,28]. A smaller ODI value
L. Ma et al.
Scheme 1. Synthetic routes of polymer semiconductors.
indicates that the orbitals are more spatially delocalized, with the or­
bitals being distributed across more atoms within the molecule [20]. The
ODI versus molecular orbital index of DPPFu-T_ × 2, DPPFu-TT_ × 2 and
DPPFu-BT_ × 2 (from LUMO +10 down to HOMO-10) was plotted for
comparison (Fig. S2). The ODI of HOMO orbitals of DPPFu-T_ × 2,
DPPFu-TT_ × 2 and DPPFu-BT_ × 2 were close to each other, suggesting
comparable delocalization of HOMO orbitals. The HOMO level of all the
three dimers was about − 4.5 eV, with their values being very close.
Despite similar ODI of HOMO orbitals in DPPFu-T_ × 2, DPPFu-TT_
× 2, and DPPFu-BT_ × 2, there was a considerable difference in the ODI
of LUMO orbitals. ODI of LUMO in DPPFu-T_ × 2 and DPPFu-TT_ × 2
was markedly lower than that in DPPFu-BT_ × 2, suggesting that LUMO
orbitals were more widely distributed in DPPFu-T_ × 2 and DPPFu-TT_
× 2 compared to DPPFu-BT_ × 2. Additionally, the LUMO orbital in
DPPFu-BT_ × 2 was primarily localized on the benzothiadiazole unit.
Despite the LUMO orbital in DPPFu-BT_ × 2 being more localized, the
LUMO level of DPPFu-BT_ × 2 was noticeably lower than that of DPPFu-
T_ × 2 and DPPFu-TT_ × 2.
Theoretical calculations were also performed on unfused models
(DPP-T_ × 2, DPP-TT_ × 2 and DPP-BT_ × 2) for comparison (Fig. S1). In
these models, the dihedral angle between DPP and adjoining thiophene
was around 10◦ , contrasting with the 0◦ angle between DPP and the
fused thiophene in the models featuring DPPFu. The fusion between DPP
3
Organic Electronics 122 (2023) 106909
and adjoining thiophenes helped to improve the coplanarity of organic
semiconductors. The HOMO level of models based on DPP was roughly
− 4.7 eV, with the fusion lifting the HOMO level by approximately 0.2
eV. The HOMO ODI of models based on DPPFu increased by varying
degrees, indicating that fusion reduced the delocalization of HOMO
orbitals. The LUMO level of DPPFu-T_ × 2 and DPPFu-TT_ × 2 was
slightly higher than that of DPP-T_ × 2 and DPP-TT_ × 2; whereas the
LUMO level of DPPFu-BT_ × 2 was slightly lower than that of DPP-BT_ ×
2. After fusion, the LUMO ODI of DPPFu-T_ × 2 and DPPFu-TT_ × 2
decreased, while that of DPPFu-BT_ × 2 increased. Fusion was beneficial
for LUMO delocalization in DPPFu-T_ × 2 and DPPFu-TT_ × 2, but it was
unfavorable for LUMO delocalization in DPPFu-BT_ × 2. In terms of
changes in the HOMO and LUMO levels, fusion decreased the HOMO-
LUMO gap by 0.2–0.3 eV. Therefore, fusion is a feasible approach to
achieving narrow-bandgap polymer semiconductors with good
planarity.
2.3. Optical and electrochemical properties
UV–vis–NIR absorption spectra for solutions and thin films of P
(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) were presented in Fig. 2
and Fig. S4. The absorption spectrum of P(DPPFu-T) and P(DPPFu-TT)
solutions showed a broad absorption range from 350 nm to 1000 nm.
L. Ma et al. Organic Electronics 122 (2023) 106909

Fig. 1. Structural formulas, optimized geometries, frontier molecular orbitals of (a) DPPFu-T_ × 2, (b) DPPFu-TT_ × 2 and (c)DPPFu-BT_ × 2.

Fig. 2. (a) UV–vis–NIR absorption spectra of polymer semiconductors in thin films; (b) cyclic voltammogram (CV) curves of polymer semiconductors.

The absorption onset of P(DPPFu-BT) solution reached 1100 nm, indi­
cating efficient intramolecular charge transfer originating from D-A
structure along the backbone. The extensional absorption of P(DPPFu-
BT) solution was attributed to the introduction of benzothiadiazole
with strong electron-withdrawing ability, which endowed the polymer
with strong electron pull-push characteristics.
Comparing with the absorption of solutions, the absorption peaks of
the corresponding thin films all red-shifted (Table 1a). The shoulder
peak was very apparent for the absorption spectrum of P(DPPFu-TT)
thin film; there was a tendency to form a shoulder peak in the absorp­
tion spectrum of P(DPPFu-T) thin film; and the shoulder peak was absent
in the absorption spectrum of P(DPPFu-BT) thin film. The shoulder peak
was greatly related to the chain interactions through π-π stacking
induced aggregation. Among the comonomers of thiophene,

4
L. Ma et al. Organic Electronics 122 (2023) 106909

Table 1a Fig. 3 displayed the 2D diffraction patterns of the thin films and Fig. 4
Optical properties of polymer semiconductors.a. presented 1D intensity profiles. In Table S4, the position of diffraction
Solution Film peaks for lamellar stacking of interdigitated alkyl chains and interchain
a π-π stacking, the corresponding distance of lamellar stacking and π-π
λmax (nm) λmax (nm) λonset (nm) Egopt (eV)
stacking, as well as the crystalline size, were summarized. The crystal
P(DPPFu-T) 420, 854 422, 785, 875 994 1.25 size perpendicular to the diffraction direction was calculated based on
P(DPPFu-TT) 420, 772 423, 764, 838 982 1.26
P(DPPFu-BT) 407, 796 418, 833 1075 1.15
the full width at half-maximum (fwhm) of (100) diffraction signals.
The 2D GIXRD analysis revealed distinct packing modes in the
a
The optical bandgap was calculated according to equation: Egopt = 1240/ polymer films (Fig. 3). The thin film of P(DPPFu-T) predominantly
exhibited a face-on packing mode; while the thin films of P (DPPFu-TT)
λonset.

and P(DPPFu-BT) primarily showed an edge-on packing mode. All the

thienothiophene and benzothiadiazole, thienothiophene was the most
beneficial for forming strong π-π interactions in P(DPPFu-TT); and
benzothiadiazole hindered the formation of strong π-π interactions in P
(DPPFu-BT).
The structural formula of polymer semiconductors made it clear that
the adjacent branched alkyl chains were in close proximity, causing
significant steric hindrance, and leading to torsion of polymer backbone,
which was detrimental to molecular organization in thin films (Scheme
1). In contrast, reducing steric hindrance could enhance molecular or­
ganization as exemplified by PDPP7T, where the branched alkyl chains
on DPP were spaced by septetthiophene. The sharp and intense shoulder
peak in the absorption spectrum of PDPP7T confirmed its excellent
molecular organization [16].
Cyclic voltammetry (CV) curves were measured to quantitatively
investigate the effect of different comonomers on the redox potential
and frontier orbital energy levels for these polymers (Fig. 2 and
Table 1b) [12]. The frontier orbital energy was calculated according to
the equation of -(4.8 + Eox/red - E(Fc/Fc+)) eV. The introduction of an
electron-withdrawing group lowered both the LUMO and HOMO levels
[29]. The electron-withdrawing ability was in the order of benzothia­
diazole > thiophene > thienothiophene. Among the polymers studied, P
(DPPFu-BT) exhibited the lowest LUMO and HOMO energy levels and
the smallest electrochemical gap.
2.4. Thin film morphology
Thin film morphology was characterized by atomic force microscopy
(AFM) (Fig. S5). All the thin films were prepared by spin coating and
exhibited fine film-forming properties. The root-mean-square (RMS)
roughness of all the thin films was about 1 nm (Table S2).
All the as-prepared films displayed a granule-like morphology,
indicating that P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT) had a ten­
dency to self-aggregate in the films. Upon thermal annealing, more
connections between granules were formed. Additionally, the granules
in P(DPPFu-TT) film grew long and thin; whereas those in P(DPPFu-BT)
grew larger.
2.5. Molecular packing
The impact of comonomer structures on interchain packing in thin
films of P(DPPFu-T), P(DPPFu-TT), and P(DPPFu-BT) was thoroughly
investigated using grazing incidence X-ray diffraction (GIXRD) [30].
Table 1b
Redox potentials and energy levels of the polymer semiconductors.
Polymer a
Eox(V) b
Ered(V) HOMO(eV) LUMO(eV)
P(DPPFu-T) 0.72 − 0.83 − 4.98 − 3.43
P(DPPFu-TT) 0.68 − 0.97 − 4.94 − 3.29
P(DPPFu-BT) 0.75 − 0.73 − 5.01 − 3.53
a conductor films were evaluated using Scherrer equation. Crystalline
Eox is the onset potential corresponding to oxidation.
b domain sizes of all the polymer semiconductors in the as-spun films were
Ered is the onset potential corresponding to reduction. HOMO is short for
highest occupied molecular orbital and LUMO is short for lowest unoccupied
molecular orbital. LUMO levels and HOMO levels are estimated from the onset
reduction and oxidation potentials, respectively. (EHOMO/LUMO = -(4.8 + Eox/
red - E(Fc/Fc+)) eV).
thin films exhibited multiple diffraction orders. Based on Figs. 3 and 4, P
(DPPFu-T) displayed anisotropic diffraction along the in-plane direction
up to the (300) diffraction peak; P(DPPFu-TT) displayed anisotropic
diffraction along the out-of-plane direction up to the (400) diffraction
peak; and P(DPPFu-BT) showed diffraction along the out-of-plane di­
rection up to the (300) diffraction peak.
A pole figure analysis of the 2D GIXRD patterns was conducted to
quantitatively investigate the stacking orientation influenced by the
comonomer unit structure (Fig. S7). Pole figures were extracted from the
(100) lamellar diffraction peaks in 2D GIXRD patterns, which were then
integrated with polar angles of 0–45◦ and 135–180◦ (Axy) representing
face-on crystallites, and 45–135◦ (Az) representing edge-on crystallites,
respectively. The integrated area of Az and Axy for these thin films were
presented in Table S3 [31,32]. The Az/Axy ratios were calculated as
34.4/65.6, 96.0/4.0 and 69.7/30.3 for the as-prepared films of P
(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT), respectively. After ther­
mal annealing at 200 ◦ C, these ratios changed to 25.3/74.7, 96.5/3.5
and 72.1/27.9. These data implied that thermal annealing increased the
packing orientation in all thin films, enhancing the face-on content in P
(DPPFu-T) and the edge-on content in P(DPPFu-TT) and P(DPPFu-BT)
thin films [33].
It is worth noting that the structural changes of comonomers from P
(DPPFu-T) to P(DPPFu-TT) and P(DPPFu-BT) resulted in polymer
semiconductors with distinct backbone orientation [34]. This variation
in orientation is likely attributed to changes in the surface energy of
polymers and their interactions with the substrate.
d-spacing and π-π stacking distance could also be obtained from 1D
GIXRD patterns (Table S4). The d-spacing values ranged from 2.32 nm to
2.67 nm, corresponding to diffraction peaks spanning from 3.3◦ to 3.8◦ .
The d-spacing strongly depended on the bisthiophene-fused DPP with
branched alkyl chains, the fully extended length of which was 3.68 nm,
and the branched alkyl chains were interdigitated in the thin films.
Among all the d-spacing values, the out-of-plane d-spacing in P
(DPPFu-TT) was the shortest. This can be attributed to the fact that
the horizontal length of thienothiophene was longer than that of thio­
phene and benzothiadiazole, resulting in reduced spatial hindrance and
a higher degree of interdigitation.
d-spacing was also related to the packing direction, which was very
obvious for P(DPPFu-BT) thin films. In this case, the in-plane d-spacing
was larger than the out-of-plane d-spacing. The π-π stacking distance for
all the polymer semiconductors was between 0.34 nm and 0.35 nm,
which was comparable with that for high-performance polymer semi­
conductors based on DPP [4,6,35].
As face-on was the dominant packing mode in P(DPPFu-T) thin film,
(100) diffraction was mainly along the in-plane direction and crystal size
ECV
g (eV)
was extracted along out-of-plane direction; edge-on packing mode was
dominant in P(DPPFu-TT) and P(DPPFu-BT) thin films, (100) was
1.55
1.65
mainly along the out-of-plane direction and crystal size was extracted
1.48 along the in-plane direction. Crystalline domain sizes in the semi­
only a few nanometers. Among them, the crystalline domain size of P
(DPPFu-TT) was the largest. This could be attributed to the longer
horizontal length of thienothiophene, which reduced steric hindrance
and facilitated better packing of segments. After thermal annealing, the

5
L. Ma et al. Organic Electronics 122 (2023) 106909

Fig. 3. Grazing incidence X-ray diffraction (GIXRD) of polymer semiconductor films. 2D GIXRD patterns of (a) P(DPPFu-T), (b) P(DPPFu-TT) and (c) P(DPPFu-BT)
thin films after thermal annealing at 200 ◦ C. Schematic illustrations for stacking orientations of (d) P(DPPFu-T), (e) P(DPPFu-TT) and (f) P(DPPFu-BT).

Fig. 4. GIXRD of polymer semiconductor films. Diffraction patterns along (a) out-of-plane and (b) in-plane directions for polymer semiconductor films after thermal
annealing at 200 ◦ C.

crystalline domain sizes of all the polymer semiconductors increased to Au was utilized as source and drain electrodes, the Fermi level of
about a dozen nanometers, which indicated improved microstructural which was well-matched with the HOMO level of polymer semi­
ordering. Therefore, thermal annealing resulted in improved carrier conductors. However, there was a significant energy difference between
transport properties of OTFTs. LUMO level of these polymer semiconductors and the Fermi level of Au.
Thermal annealing made the contact between semiconductors and
electrodes more compact, which facilitated the tunneling injection of
2.6. Organic field-effect transistors
electrons from electrodes to semiconductors. As a result, the thermal
annealing process contributed to the improved performance and charge
Charge transport properties of these polymer semiconductors were
transport properties of OFETs in this study.
evaluated using bottom-gate/bottom-contact (BGBC) OFETs. All the
Electron transport of polymer semiconductors was also favorable.
OFETs exhibited ambipolar charge transport property in the N2 atmo­
LUMO ODI values of all the model compounds (Fig. 1) were small,
sphere. The charge mobility (μh and μe), on/off current ratio (Ion/Ioff)
indicating well delocalized LUMO orbitals. LUMO ODI values were even
and threshold voltage (VT) were measured and compared for OTFTs
smaller than HOMO ODI values for DPPFu-T_ × 2 and DPPFu-TT_ × 2.
based on both as-prepared films and thermally annealed films (Table 2).
The delocalization not only facilitated charge transport along polymer
OTFTs based on as-prepared films exhibited hole-dominated charge
chains, but also promoted charge hopping between polymer chains
transport property, with the hole mobility being approximately 3–10
through favorable intermolecular coupling.
times higher than the electron mobility. After thermal annealing at
The electron and hole mobilities of P(DPPFu-T) were on the order of
200 ◦ C, the electron transport properties of all the polymer semi­
10− 3 cm2V− 1s− 1, and those of P(DPPFu-TT) and P(DPPFu-BT) were on
conductors were significantly improved. As a result, all the OFETs
the order of 10− 2 cm2V− 1s− 1 magnitude. P(DPPFu-T) exhibited electron-
exhibited clear ambipolar charge transport characteristics (Fig. 5).

Table 2
Performance parameters of bottom-gate/bottom-contact (BGBC) OFETs based on P(DPPFu-T), P(DPPFu-TT) and P(DPPFu-BT).
p-channel n-channel μe/μh
μh (cm2V− 1s− 1) Ion/Ioff VT (V) μe (cm2V− 1s− 1) Ion/Ioff VT (V)
3
P(DPPFu-T) as prepared 2.6 × 10− 2.6 × 103 8 2.7 × 10− 4
4.7 × 10 62 0.11
3
thermal annealing 2.4 × 10− 5.7 × 103 − 12 6.7 × 10− 3
3.4 × 104 58 2.79
2
P(DPPFu-TT) as prepared 6.3 × 10− 3.1 × 102 13 8.4 × 10− 3
3.3 × 10 85 0.13
2
thermal annealing 9.8 × 10− 3.2 × 103 − 27 7.5 × 10− 2
1.4 × 103 55 0.76
4
P(DPPFu-BT) as prepared 1.5 × 10− 1.4 × 103 3 5.0 × 10− 5
5.4 × 10 45 0.33
2
thermal annealing 1.6 × 10− 1.6 × 104 − 27 1.7 × 10− 2
7.7 × 103 51 1.06

The parameters were extracted from the devices with performance of medium level among at least 5 devices.

6
L. Ma et al.
Fig. 5. Output and transfer curves of OFETs based on P(DPPFu-T) (a, b), P(DPPFu-TT) (c, d) and P(DPPFu-BT) (e, f).
dominated transport, while P(DPPFu-TT) and P(DPPFu-BT) showed a
balanced electron and hole transport property. Especially, P(DPPFu-BT)
demonstrated ideally balanced charge carrier mobilities for both elec­
trons and holes. DPPFu proved to be a suitable building block for the
preparation of copolymer semiconductors with ambipolar charge
transport capabilities.
It is worth mentioning that charge transport performance of these
polymer semiconductors was inferior when compared to prevailing
high-performance semiconductors. The primary reason for this limita­
tion was the bulky side chains, which caused significant spatial hin­
drance. This hindrance reduced the planarity of the polymer backbones
and hindered the orderly packing of polymer chains, leading to
compromised charge transport properties.
3. Conclusion
A series of polymer semiconductors, namely P(DPPFu-T), P(DPPFu-
TT) and P(DPPFu-BT), were successfully synthesized. These polymer
semiconductors displayed remarkable thermal stability, broad absorp­
tion in the UV–Vis–NIR range, and exhibited ambipolar charge transport
properties.
Among the three polymer semiconductors, P(DPPFu-TT) exhibited
the highest Mn, reaching 56.0 kg/mol. The HOMO and LUMO were the
most delocalized in the model DPPFu-TT_ × 2. Thin films of P(DPPFu-
TT) predominantly adopted an edge-on packing mode, with an edge-
on/face-on ratio of 96.5/3.5. Charge transport properties of P(DPPFu-
TT) were superior to the other two polymer semiconductors, owing to
its high molecular weight, delocalized frontier orbitals and the orga­
nized arrangement of polymer chains. The hole and electron mobilities
of P(DPPFu-TT) were 9.8 × 10− 2 and 7.5 × 10− 2 cm2V− 1s− 1,
respectively.
In contrast, the Mn value of P(DPPFu-BT) was the lowest. Unlike
DPPFu-T_ × 2 and DPPFu-TT_ × 2, the LUMO level in DPPFu-BT_ × 2 was
more localized than the HOMO level. Thin films of P(DPPFu-BT) pre­
dominantly exhibited an edge-on packing mode, with an edge-on/face-
on ratio of 72.1/27.9. P(DPPFu-BT) demonstrated ideally balanced
7
Organic Electronics 122 (2023) 106909
charge transport properties, with hole and electron mobilities measured
at 1.6 × 10− 2 cm2V− 1s− 1 and 1.7 × 10− 2 cm2V− 1s− 1, respectively.
Distinctly, thin film of P(DPPFu-T) mainly adopted a face-on packing
mode, with an edge-on/face-on ratio of 25.3/74.7, differing from P
(DPPFu-TT) and P(DPPFu-BT) thin films. P(DPPFu-T) displayed
electron-dominated charge transport properties, with the electron
mobility approximately two times higher than hole mobility. This sug­
gests that the face-on packing mode potentially favors electron
transport.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work was supported by Beijing Municipal Science and Tech­
nology Project (KM201910017003), the Project of Cultivation for young
top-notch Talents of Beijing Municipal Institutions (BPHR202203093),
Young Elite Scientists Sponsorship Program by BAST (BYESS2023089)
and Beijing Natural Science Foundation (2174074) and URT
(2019J00031 and 2023J00074) program.
The GIXRD data were obtained at BSRF-1W1A. The authors grate­
fully acknowledge the cooperation of the beamline scientists at BSRF-
1W1A beamline.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.orgel.2023.106909.
L. Ma et al. Organic Electronics 122 (2023) 106909

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